Determining wavelength-dependent quantum yields of photodegradation: importance of experimental setup and reference values for actinometers.

Accurate quantum yields are crucial for modeling photochemical reactions in natural and engineered treatment systems. Quantum yields are usually determined using a single representative light source such as xenon lamps to mimic sunlight or UVC light for water treatment. However, photodegradation modeling can be improved by understanding the wavelength dependence of quantum yields and the potential errors introduced by the experimental setup. In this study, we investigated the effects of experimental setup on measured quantum yields using four photoreactor systems and up to 11 different light sources. When using a calibrated spectroradiometer to measure incident irradiance on an open solution surface, apparent quantum yields were up to two times higher if light reflection and light screening were not accounted for in the experimental setup. When the experimental setup was optimized to allow for accurate irradiance measurements, quantum yields were reproducible across photoreactors. The optimized experimental setup was then used to determine quantum yields of uridine, atrazine, p-nitroanisole (PNA), sulfamethoxazole, and diclofenac across the UV spectrum. No significant wavelength dependence of quantum yields was observed for sulfamethoxazole and diclofenac, in contrast to wavelength-dependent quantum yields for uridine, atrazine, and PNA. These reference values can be used for determining wavelength-dependent quantum yields of other compounds of interest. Additionally, more accurate results can be obtained when using (1) an actinometer with similar light absorption and photoreactivity compared to that of the target chemical, (2) optically transparent actinometer solutions that can account for light reflection within reaction vessels, and (3) a quantum yield that corresponds to the spectrum of the selected light source.

Emerging investigator series: quantifying the impact of cloud cover on solar irradiance and environmental photodegradation.

Environmental photodegradation is dependent on the solar irradiance that reaches the Earth's surface, and photodegradation half-lives of contaminants are typically estimated assuming clear sky (i.e., cloudless) conditions. In this work, the effect of cloud cover on solar irradiance was investigated. Data from the National Renewable Energy Laboratory (NREL), which spanned 3 years of observations (10/2017 to 12/2020), were used to train two machine learning models to predict irradiance based on three inputs - day of year, time of day, and percentage of the sky that was cloudy. Results showed a non-linear relationship between cloud cover and irradiance. Solar irradiance was minimally impacted up to ≈50% cloud cover but decreased by ≈67% at 100% cloud cover. Both random forest and artificial neural network models performed well with relative root mean squared errors of 26-31%, which varied depending on the source of cloud cover data and the spectral region being modeled. Daily irradiance values for a whole year were predicted for varying cloud conditions using the machine learning models; this result was approximated using a quadratic fit of y = 1 - 0.00243x - (4.24 × 10-5)x2 where y is the fraction of clear sky irradiance expected and x is the percentage of cloud cover in the sky. In addition, the model results supported that there was no wavelength dependence for the effect of cloud cover. Therefore, decreases in both direct and indirect photodegradation rates should be proportional to the decrease in irradiance, which has a non-linear dependence on cloud cover.

Factors affecting the mixed-layer concentrations of singlet oxygen in sunlit lakes.

The steady-state concentration of singlet oxygen within a lake ([1O2]SS) is an important parameter that can affect the environmental half-life of pollutants and environmental fate modelling. However, values of [1O2]SS are often determined for the near-surface of a lake, and these values typically do not represent the average over the epilimnia of lakes. In this work, the environmental and physical factors that have the largest impact on [1O2]SS within lake epilimnia were identified. It was found that the depth of the epilimnion has the largest impact on depth-averaged [1O2]SS, with a factor of 8.8 decrease in [1O2]SS when epilimnion depth increases from 2 m to 20 m. The next most important factors are the wavelength-dependent singlet oxygen quantum yield relationship and the latitude of the lake, causing variations in [1O2]SS by factors of 3.2 and 2.5 respectively, over ranges of representative values. For a set of representative parameters, the depth-averaged value of [1O2]SS within an average epilimnion depth of 9.0 m was found to be 5.8 × 10-16 M and the near-surface value of [1O2]SS was found to be 1.9 × 10-14 M. We recommend a range of 6 × 10-17 to 5 × 10-15 M as being more representative of [1O2]SS values within the epilimnia of lakes globally and potentially more useful for estimating pollutant lifetimes than those calculated using [1O2]SS values that correspond to near-surface, summer midday values. This work advances our understanding of [1O2]SS inter-lake variability in the environment, and provides estimates of [1O2]SS for practitioners and researchers to assess environmental half-lives of pollutants due to reaction with singlet oxygen.

Photochemical fate of medetomidine in coastal and marine environments.

Medetomidine has been authorized in ship hull paints as an antifouling biocide under the biocidal product regulation in Europe since 2016. Its release into marine systems causes concerns over persistence and toxicity. However, the environmental fate of medetomidine has not been fully investigated. In this study, the photodegradation of medetomidine under natural sunlight conditions was investigated using collected coastal and sea waters. In addition, the phototransformation of medetomidine with reactive species (i.e., singlet oxygen, excited triplet state organic matter, and hydroxyl radicals) under UVA light was examined. Photoproducts were isolated by high-performance liquid chromatography (HPLC), identified by a combination of nuclear magnetic resonance (NMR) spectroscopy and time-of-flight mass spectrometry (qTOF), and reaction mechanisms were proposed. The results show that medetomidine is a neutral base (pKa of protonated form = 7.2) that leads to two different protonation states in the aquatic environment. Photodegradation of neutral medetomidine was dominated by reaction with singlet oxygen, while protonated medetomidine was relatively photostable. The contribution of reactive species to the overall photodegradation of neutral medetomidine was calculated to provide an assessment of phototransformation of medetomidine. The half-live of medetomidine was < 1.5 days in natural waters (pHcoastal = 8.3; pHsea = 8.1) under sunlit near-surface conditions, suggesting that it is not persistent in the aquatic environment. Because medetomidine has a relatively short half-life in sunlit aquatic ecosystems, a number of products, such as 2-(2,3-dimethylphenyl)propanamide, can be formed by photochemical reactions of medetomidine, with unknown consequences for marine and coastal waters.

Linking Triclosan's Structural Features to Its Environmental Fate and Photoproducts.

Triclosan is a high-production volume chemical, which has become widely detected in environmental systems because of its widespread usage. Photodegradation has been identified as a major degradation pathway, but the identified photoproducts are also chemicals of concern. In this study, lower chlorinated derivatives of triclosan were synthesized to investigate the impact the chlorine substituents have on the photodegradation rate and the photoproducts produced. In addition, the photodegradation of two classes of photoproducts-dibenzo-p-dioxins (DDs) and 2,2'-dihydroxylated biphenyls-was also investigated. Degradation of triclosan in near-surface sunlit waters was relatively fast (t1/2 < 5 h). Calculated degradation rates were slower for DDs and faster for dihydroxylated biphenyls in comparison to that for triclosan. In addition, the 2'-Cl substituent was critical for the high quantum yield measured for triclosan and necessary for the photodegradation mechanism that forms DDs and dihydroxylated biphenyls. The 4-Cl substituent was responsible for higher rates of light absorption and the environmentally relevant pKa. Without either of these substituents, the environmental fate of triclosan would be markedly different.

Correction: Updated and validated solar irradiance reference spectra for estimating environmental photodegradation rates.

Correction for 'Updated and validated solar irradiance reference spectra for estimating environmental photodegradation rates' by Jennifer N. Apell and Kristopher McNeill, Environ. Sci.: Processes Impacts, 2019, 21, 427-437.

A streamlined workflow to study direct photodegradation kinetic and transformation products for persistence assessment of a fragrance ingredient in natural waters.

Photodegradation can be an important abiotic degradation process to consider for the fate and persistence assessment of chemical substances in the environment. In this work, using a fragrance ingredient (FI, (E)-4-(2,2,3,6-tetramethylcyclohexyl)but-3-en-2-one) as an example, we developed a streamlined workflow to investigate direct photodegradation of chemicals in the aquatic environment, including laboratory investigation of kinetics and transformation products and estimation of its aquatic environmental half-lives. Direct photodegradation was determined to be the dominant photodegradation process for FI with a quantum yield of 0.25, which was supported by photodegradation experiments conducted in natural sunlight. Accounting for light attenuation by dissolved organic matter in natural waters of different depths resulted in aquatic half-lives of <31 days even at polar latitudes. Photoisomerization was shown to be a major photodegradation pathway along with the formation and subsequent degradation of constitutional isomers and photooxidation products. These results contributed to FI being assessed as non-persistent in the environment.

Photodegradation of Fludioxonil and Other Pyrroles: The Importance of Indirect Photodegradation for Understanding Environmental Fate and Photoproduct Formation.

Fludioxonil is a pyrrole-containing pesticide whose registration as a plant protection product is currently under review in the United States and Europe. There are concerns over its potential persistence and toxicity in the aquatic environment; however, the pyrrole moiety represents a potential reaction site for indirect photodegradation. In this study, the direct and indirect photodegradation of fludioxonil, along with pyrrole, 3-cyanopyrrole, and 3-phenylpyrrole, were investigated. Results showed that pyrrole moieties are capable of undergoing direct photoionization and sensitized photooxidation to form radical cation species, which then likely deprotonate and react with dissolved oxygen. Additionally, pyrrole moieties can undergo reactions with singlet oxygen (1O2). Furthermore, the presence of electron-withdrawing or -donating substituents substantially impacted the reaction rate with 1O2 as well as the one-electron oxidation potential of the pyrrole that dictates reactions with triplet states of dissolved organic matter (3CDOM*). For fludioxonil, which can undergo both direct and indirect photodegradation, the reaction rate constant with 1O2 alone resulted in a predicted t1/2 < 2 days in waters under sunlit near-surface conditions, suggesting it will not be persistent in aquatic systems. These results are useful for evaluating the environmental fate of fludioxonil as well as other pyrrole compounds.

Toward Sustainable Environmental Quality: Priority Research Questions for North America.

Anticipating, identifying, and prioritizing strategic needs represent essential activities by research organizations. Decided benefits emerge when these pursuits engage globally important environment and health goals, including the United Nations Sustainable Development Goals. To this end, horizon scanning efforts can facilitate identification of specific research needs to address grand challenges. We report and discuss 40 priority research questions following engagement of scientists and engineers in North America. These timely questions identify the importance of stimulating innovation and developing new methods, tools, and concepts in environmental chemistry and toxicology to improve assessment and management of chemical contaminants and other diverse environmental stressors. Grand challenges to achieving sustainable management of the environment are becoming increasingly complex and structured by global megatrends, which collectively challenge existing sustainable environmental quality efforts. Transdisciplinary, systems-based approaches will be required to define and avoid adverse biological effects across temporal and spatial gradients. Similarly, coordinated research activities among organizations within and among countries are necessary to address the priority research needs reported here. Acquiring answers to these 40 research questions will not be trivial, but doing so promises to advance sustainable environmental quality in the 21st century. Environ Toxicol Chem 2019;38:1606-1624. © 2019 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

Updated and validated solar irradiance reference spectra for estimating environmental photodegradation rates.

Irradiance reference spectra are used to calculate environmentally relevant photodegradation half-lives, but the currently used spectra were originally published in the 1980s with limited validation. The goal of this work is to provide updated irradiance reference spectra using the Simple Model of the Atmospheric Radiative Transfer of Sunshine (SMARTS). The SMARTS irradiance spectra were validated against measurements from several high-resolution spectroradiometers, and the updated irradiance reference spectra use current measurements for atmospheric species that can affect the irradiance that reaches the Earth's surface. These updated irradiance spectra are provided in 1 nm increments from 280 to 800 nm for 0° to 70° latitude at 10° increments in both the northern and southern hemisphere. Lastly, the influence of the input parameters on the modeled irradiance spectra was investigated. This work will allow users to calculate more accurate photodegradation half-lives using the updated irradiance reference spectra, and it also provides insight for users to calculate their own location- and time-specific irradiance spectra using SMARTS.

Investigating the Effect of Bioirrigation on In Situ Porewater Concentrations and Fluxes of Polychlorinated Biphenyls Using Passive Samplers.

Polychlorinated biphenyl (PCB) fluxes from contaminated sediments can be caused by mechanisms including diffusion, bioirrigation, and resuspension, but it is often unclear which mechanisms are important. In the Lower Duwamish Waterway (Seattle, Washington), the presence of abundant benthic macrofauna suggests that porewater bioirrigation may be an important mechanism for PCB transport from the bed into the overlying water column. In this field study, the fluxes of PCBs due to bioirrigation were quantified by using (a) polyethylene (PE) samplers to quantify in situ and ex situ (i.e., equilibrium) PCB porewater concentration profiles and (b) measurements of the geochemical tracer 222Rn to quantify the rate of porewater exchange with overlying water. The results showed that bioirrigation caused sorptive disequilibrium with the surrounding sediment, which led to lower in situ porewater concentrations than expected from sediment concentrations. The combined fluxes of seven PCB congeners (Σ7PCBs) were 1.6-26 ng/m2/day for the three field sites, similar in magnitude to the upper limit estimates of diffusive fluxes calculated assuming water-side boundary layer control (Σ7PCBs = 1.3-47 ng/m2/day). Moreover, the depleted in situ porewater concentrations imply lower diffusive flux estimates than if the ex situ porewater concentrations had been used to estimate fluxes (Σ7PCBs = 89-670 ng/m2/day). These results suggest that nondiffusive PCB fluxes from the sediment bed are occurring and that quantifying in situ porewater concentrations is crucial for accurately quantifying both diffusive and nondiffusive PCB fluxes.

Advancing the Use of Passive Sampling in Risk Assessment and Management of Sediments Contaminated with Hydrophobic Organic Chemicals: Results of an International Ex Situ Passive Sampling Interlaboratory Comparison.

This work presents the results of an international interlaboratory comparison on ex situ passive sampling in sediments. The main objectives were to map the state of the science in passively sampling sediments, identify sources of variability, provide recommendations and practical guidance for standardized passive sampling, and advance the use of passive sampling in regulatory decision making by increasing confidence in the use of the technique. The study was performed by a consortium of 11 laboratories and included experiments with 14 passive sampling formats on 3 sediments for 25 target chemicals (PAHs and PCBs). The resulting overall interlaboratory variability was large (a factor of ∼10), but standardization of methods halved this variability. The remaining variability was primarily due to factors not related to passive sampling itself, i.e., sediment heterogeneity and analytical chemistry. Excluding the latter source of variability, by performing all analyses in one laboratory, showed that passive sampling results can have a high precision and a very low intermethod variability (

Polychlorinated biphenyl (PCB) contamination in Galveston Bay, Texas: Comparing concentrations and profiles in sediments, passive samplers, and fish.

The industrialized portion of the Houston Ship Channel (HSC) is heavily contaminated with anthropogenic contaminants, most prominent of which are the polychlorinated biphenyls (PCBs). This contamination has driven adaptive evolution in a keystone species for Galveston Bay, the Gulf killifish (Fundulus grandis). We investigated the geographical extent of PCB impacts by sampling 12 sites, ranging from the heavily industrialized upper portion of the HSC to Galveston Island. At each site, PCB concentrations and profiles were determined in three environmental compartments: sediment, water (polyethylene passive samplers), and fish tissue (resident Gulf killifish). We observed a steep gradient of PCB contamination, ranging from 4.00 to 100,000 ng/g organic carbon in sediment, 290-110,000 ng/g lipid in fish, and 4.5-2300 ng/g polyethylene in passive samplers. The PCB congener profiles in Gulf killifish at the most heavily contaminated sites were shifted toward the higher chlorinated PCBs and were highly similar to the sediment contamination profiles. In addition, while magnitude of total PCB concentrations in sediment and total fish contamination levels were highly correlated between sites, the relative PCB congener profiles in fish and passive samplers were more alike. This strong correlation, along with a lack of dependency of biota-sediment accumulation factors with total contamination rates, confirm the likely non-migratory nature of Gulf killifish and suggest their contamination levels are a good site-specific indicator of contamination in the Galveston Bay area. The spatial gradient of PCB contamination in Galveston Bay was evident in all three matrices studied and was observed effectively using Gulf killifish contamination as an environmentally relevant bioindicator of localized contamination in this environment.

Assessment of Ambient Exposures Firefighters Encounter While at the Fire Station: An Exploratory Study.

OBJECTIVE: Firefighters are at an increased risk for many types of cancer. Although most studies on this topic focus on exposures encountered while fighting fires, exposures at the fire station are also cause for concern. This pilot study aimed to describe air quality within a few fire stations in and around Boston, Massachusetts, and to investigate physical and organizational factors that may influence levels of contaminants in stations. METHODS: Air sampling of particulate matter less than 2.5 µm in diameter (PM2.5) and particle-bound polycyclic aromatic hydrocarbons (PAHs) was completed at four fire stations in Spring, 2016. Sampling occurred in the kitchen, truck bay, and just outside the station. Data were analyzed to assess differences between and within stations. Interviews (n =7) were conducted with officers at each station to explore health and safety-related organizational policies and practices. Interviews were transcribed and analyzed for thematic content. RESULTS: At each station, levels of contaminants were higher in the truck bays than either the outdoors or kitchen, and varied the most throughout the day. The station with the highest exposures in the truck bay had the lowest levels in the kitchen, which was possibly explained by new building materials and effective separation between building zones. The age and layout of the stations appeared to determine the extent to which policies favoring exhaust capture were implemented. CONCLUSION: Levels of PM2.5 and PAH inside fire stations may contribute to firefighter cancer risk. Through understanding contaminant variability, we can begin to design and test interventions that improve cancer prevention.

The atmosphere as a source/sink of polychlorinated biphenyls to/from the Lower Duwamish Waterway Superfund site.

Waterbodies polluted with polychlorinated biphenyls (PCBs) may cause the air in the surrounding area to become PCB-contaminated. Conversely, when a waterbody is located in or near an urban area, the deposition of atmospheric PCBs may act as a low-level, ongoing source of PCB contamination to that water. Distinguishing these situations is necessary to be protective of human populations and to guide efforts seeking to cleanup such aquatic ecosystems. To assess the situation at the Lower Duwamish Waterway (LDW) Superfund site, low-density polyethylene passive samplers were deployed in the summer of 2015 to quantify freely dissolved water and gaseous air concentrations of PCBs thereby enabling estimates of the direction and magnitude of air-water exchange of PCB congeners. For the sum of the 27 PCB congeners, average concentrations were 220 pg/m3 (95% C.I.: 80-610) in the air and 320 pg/L (95% C.I.: 110-960) in the water. The sum of air-water exchange fluxes of these PCB congeners was estimated to be 68 ng/m2/day (95% C.I.: 30-148) into the lower atmosphere, contrasting with the reported wet and dry depositional flux of only 5.5 ng/m2/day (95% C.I.: 1-38) from the air into the water. Therefore, the atmosphere was ultimately a sink of PCBs from the LDW Superfund site, at least under 2015 summertime conditions. However, we conclude that air-water exchange of PCBs is likely only a minor sink of PCBs from the LDW and only a minor source of contamination to the region's local atmosphere.

In situ passive sampling of sediments in the Lower Duwamish Waterway Superfund site: Replicability, comparison with ex situ measurements, and use of data.

Superfund sites with sediments contaminated by hydrophobic organic compounds (HOCs) can be difficult to characterize because of the complex nature of sorption to sediments. Porewater concentrations, which are often used to model transport of HOCs from the sediment bed into overlying water, benthic organisms, and the larger food web, are traditionally estimated using sediment concentrations and sorption coefficients estimated using equilibrium partitioning (EqP) theory. However, researchers have begun using polymeric samplers to determine porewater concentrations since this method does not require knowledge of the sediment's sorption properties. In this work, polyethylene passive samplers were deployed into sediments in the field (in situ passive sampling) and mixed with sediments in the laboratory (ex situ active sampling) that were contaminated with polychlorinated biphenyls (PCBs). The results show that porewater concentrations based on in situ and ex situ sampling generally agreed within a factor of two, but in situ concentrations were consistently lower than ex situ porewater concentrations. Imprecision arising from in situ passive sampling procedures does not explain this bias suggesting that field processes like bioirrigation may cause the differences observed between in situ and ex situ polymeric samplers.

Understanding the rates of nonpolar organic chemical accumulation into passive samplers deployed in the environment: Guidance for passive sampler deployments.

Polymeric passive samplers have become a common method for estimating freely dissolved concentrations in environmental media. However, this approach has not yet been adopted by investigators conducting remedial investigations of contaminated environmental sites. Successful adoption of this sampling methodology relies on an understanding of how passive samplers accumulate chemical mass as well as developing guidance for the design and deployment of passive samplers. Herein, we outline the development of a simple mathematical relationship of the environmental, polymer, and chemical properties that control the uptake rate. This relationship, called a timescale, is then used to illustrate how each property controls the rate of equilibration in samplers deployed in the water or in the sediment. Guidance is also given on how to use the timescales to select an appropriate polymer, deployment time, and suite of performance reference compounds. Integr Environ Assess Manag 2016;12:486-492. © 2015 SETAC.

Modeling the transport of organic chemicals between polyethylene passive samplers and water in finite and infinite bath conditions.

Understanding the transfer of chemicals between passive samplers and water is essential for their use as monitoring devices of organic contaminants in surface waters. By applying Fick's second law to diffusion through the polymer and an aqueous boundary layer, the authors derived a mathematical model for the uptake of chemicals into a passive sampler from water, in finite and infinite bath conditions. The finite bath model performed well when applied to laboratory observations of sorption into polyethylene (PE) sheets for various chemicals (polycyclic aromatic hydrocarbons, polychlorinated biphenyls [PCBs], and dichlorodiphenyltrichloroethane [DDT]) and at varying turbulence levels. The authors used the infinite bath model to infer fractional equilibration of PCB and DDT analytes in field-deployed PE, and the results were nearly identical to those obtained using the sampling rate model. However, further comparison of the model and the sampling rate model revealed that the exchange of chemicals was inconsistent with the sampling rate model for partially or fully membrane-controlled transfer, which would be expected in turbulent conditions or when targeting compounds with small polymer diffusivities and small partition coefficients (e.g., phenols, some pesticides, and others). The model can be applied to other polymers besides PE as well as other chemicals and in any transfer regime (membrane, mixed, or water boundary layer-controlled). Lastly, the authors illustrate practical applications of this model such as improving passive sampler design and understanding the kinetics of passive dosing experiments.

Validating the use of performance reference compounds in passive samplers to assess porewater concentrations in sediment beds.

Hydrophobic organic compounds (HOCs) like polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) tend to accumulate in sediment beds when they are released into aquatic environments. Due to this buildup of HOCs in the sediment, the highest water concentrations are often in the pore water. Passive samplers can be used in the field (i.e., in situ) to measure freely dissolved porewater concentrations if target contaminants diffusing through the sediment and into the sampler exhibit the same diffusive retardation factors as performance reference compounds (PRCs) that are diffusing out of the sampler and into the sediment. To test this assumption, polyethylene (PE) passive samplers were placed in an organic- and black- carbon-rich sediment bed in the laboratory with samplers removed every 30 days for 4 months. The concentrations of target contaminants in the PE at each time point, corrected using measures of the losses of PRCs, were in good agreement with separately measured equilibrium concentrations in a well-mixed system. Concentrations in the PE passive samplers, normalized by their polyethylene-water partition coefficients, were also in good agreement with directly measured porewater concentrations. Finally, PE-deduced porewater concentrations were compared with the traditional equilibrium partitioning models and showed that considering sorption to only organic carbon substantially overestimated porewater concentrations. However, predictions improved greatly if sorption to black carbon was also considered.

Combined ion exchange treatment for removal of dissolved organic matter and hardness.

Dissolved organic matter (DOM) and hardness cations are two common constituents of natural waters that substantially impact water treatment processes. Anion exchange treatment, and in particular magnetic ion exchange (MIEX), has been shown to effectively remove DOM from natural waters. An important advantage of the MIEX process is that it is used as a slurry in a completely mixed flow reactor at the beginning of the treatment train. Hardness ions can be removed with cation exchange resins, although typically using a fixed bed reactor at the end of a treatment train. In this research, the feasibility of combining anion and cation exchange treatment in a single completely mixed reactor for treatment of raw water was investigated. The sequence of anion and cation exchange treatment, the number of regeneration cycles, and the chemistry of the regeneration solution were systematically explored. Simultaneous removal of DOM (70% as dissolved organic carbon) and hardness (>55% as total hardness) was achieved by combined ion exchange treatment. Combined ion exchange is expected to be useful as a pre-treatment for membrane systems because both DOM and divalent cations are major foulants of membranes.